Fabric article treatment composition for use in a lipophilic fluid system

ABSTRACT

A fabric article treatment composition comprising a polar solvent and a hydrophobic surfactant, wherein the composition is miscible in a lipophilic fluid is provided.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. ProvisionalApplication Ser. No. 60/483,346, filed on Jun. 27, 2003.

FIELD OF THE INVENTION

[0002] The present invention relates to a fabric article treatmentcomposition, more particularly a fabric article treatment compositionsuitable for use in a lipophilic fluid-based fabric article treatingsystem and methods for using the fabric article treatment composition.

BACKGROUND OF THE INVENTION

[0003] Conventional water-based fabric article treating systems haveutilized hydrophilic pretreating compositions that are effective atremoving and/or reducing hydrophilic stains.

[0004] Conventional dry cleaning systems have utilized hydrophobicpretreating compositions that are effective at removing and/or reducinghydrophobic stains.

[0005] Recently, formulators have been exploring lipophilic fluid-basedfabric article treating systems. Removal of hydrophilic stains in suchlipophilic fluid-based systems has been a challenge. Accordingly, thereis a need for a fabric article treatment composition that is effectiveat removing hydrophilic stains from fabric articles wherein the fabricarticles are then subjected to a lipophilic fluid-based fabric articletreating system.

SUMMARY OF THE INVENTION

[0006] The present invention fulfills the need described above byproviding a fabric article treatment composition that is miscible in alipophilic fluid.

[0007] In one aspect of the present invention, a fabric articletreatment composition comprising:

[0008] a) a polar solvent exhibiting at least one of the followingHansen solubility parameters:

[0009] i) a fractional polar value (f_(P)) of greater than 0.02; and/or

[0010] ii) a fractional hydrogen bonding value (f_(H)) of greater than0.10; and

[0011] b) a hydrophobic surfactant;

[0012] wherein the fabric article treatment composition is miscible in alipophilic fluid, is provided.

[0013] In another aspect of the present invention, an article ofmanufacture comprising:

[0014] a) a container; and

[0015] b) a fabric article treatment composition according to thepresent invention contained within the container, is provided.

[0016] In still another aspect of the present invention, a method forremoving a hydrophilic stain from a fabric article in need of treatment,the method comprising contacting the hydrophilic stain with a fabricarticle treatment composition that is miscible in a lipophilic fluid toform a pretreated fabric article, is provided.

[0017] In yet another aspect of the present invention, a fabric articletreated by a method in according to the present invention, is provided.

[0018] Accordingly, the present invention provides a fabric articletreatment composition, an article of manufacture comprising the fabricarticle treatment composition, a method for treating a fabric articlewith the fabric article treatment composition and a fabric articletreated by such a method.

DETAILED DESCRIPTION OF THE INVENTION

[0019] Definitions

[0020] “Fabric article” as used herein is intended to mean any articlethat is customarily cleaned in a conventional laundry process or in adry cleaning process. As such the term encompasses articles of clothing,linen, drapery, and clothing accessories. The term also encompassesother items made in whole or in part of fabric, such as tote bags,furniture covers, tarpaulins and the like.

[0021] “Stain” means any undesirable substance on a fabric article thatis desired to be removed. Generally, stains are found only on a portionof the article and are generated by accidental contact between the soiland the fabric article. By the term “hydrophilic stains” it is meantthat the stain is comprised of water at the time it first came incontact with the fabric article, or the stain retains a significantportion of water on the fabric article. Examples of hydrophilic stainsinclude, but are not limited to, beverages, many food soils, watersoluble dyes, bodily fluids such as sweat, urine or blood, outdoor soilssuch as grass stains and mud.

[0022] “Miscible” as used herein means that greater than 5% and/orgreater than 20% and/or greater than 50% by weight of a material issoluble in and/or dispersible in another material. For example thatgreater than 5% by weight of the fabric article treatment composition ofthe present invention is soluble in and/or dispersible in a lipophilicfluid.

[0023] “Pretreated fabric article” as used herein means a fabric articlethat has been contacted with a fabric article treatment composition ofthe present invention prior to subsequent contact with a discretelipophilic fluid.

[0024] “Discrete lipophilic fluid” as used herein means a lipophilicfluid that is not part of the neat fabric article treatment composition.Typically, the discrete lipophilic fluid when combined with the fabricarticle treatment composition makes up greater than 30% and/or greaterthan 50% and/or greater than 70% by weight of the fabric articletreatment composition. Notwithstanding the above, a lipophilic fluid canbe present in a neat fabric article treatment composition (such as in aproduct that a consumer purchases and uses to contact a stain on afabric article in a pretreating step prior to subjecting the pretreatedfabric article to a fabric article treating process, such as alipophilic fluid-based system).

[0025] “Weight average molecular weight” as used herein means the weightaverage molecular weight as determined using gel permeationchromatography according to the protocol found in Colloids and SurfacesA. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121.

[0026] Fabric Article Treatment Composition

[0027] The fabric article treatment composition comprises a polarsolvent and a hydrophobic surfactant, wherein the fabric articletreatment composition is miscible in a lipophilic fluid.

[0028] In one embodiment, the fabric article treatment compositioncomprises from about 10% to about 99.9% and/or from about 20% to about95% and/or from about 30% to about 90% by weight of the fabric articletreatment of the polar solvent.

[0029] In another embodiment, the fabric article treatment compositioncomprises from about 0.1% to about 90% and/or from about 5% to about 80%and/or from about 10% to about 80% and/or from about 10% to about 30% byweight of the fabric article treatment composition of the hydrophobicsurfactant.

[0030] In still another embodiment, the fabric article treatmentcomposition comprises the polar solvent and the hydrophobic surfactantat a weight ratio of polar solvent to hydrophobic surfactant of fromabout 10:1 to about 1:10 and/or from about 10:1 to about 1:5 and/or fromabout 5:1 to about 1:1.

[0031] In yet another embodiment, the fabric article treatmentcomposition has a flash point of greater than 37° C. and/or greater than50° C.

[0032] In one embodiment, a neat fabric article treatment composition,such as that contained in a container or some other delivery deviceprior to contacting the fabric comprises:

[0033] a. from about 5% to about 99.9% and/or from about 10% to about40% by weight of the fabric article treatment composition of a polarsolvent; and

[0034] b. from about 0.1% to about 90% and/or from about 10% to about40% by weight of the fabric article treatment composition of ahydrophobic surfactant.

[0035] In another embodiment, a fabric article treatment composition, inuse, such as when the pretreated fabric article is contacted with adiscrete lipophilic fluid, comprises:

[0036] a. from about 1% to about 99% and/or from about 5% to about 40%by weight of the fabric article treatment composition of a polarsolvent;

[0037] b. from about 0.1% to about 90% and/or from about 5% to about 40%by weight of the fabric article treatment composition of a hydrophobicsurfactant; and

[0038] c. from about 0.1% to about 95% and/or from about 5% to about 50%by weight of the fabric article treatment composition of a lipophilicfluid.

[0039] In other embodiments, the fabric article treatment compositioncomprises a polar solvent and a hydrophobic surfactant at a ratio ofpolar solvent to hydrophobic surfactant of from about 20:1 to about 1:20and/or from about 10:1 to about 1:10.

[0040] Preferred fabric article treatment composition suitable for useherein can further be qualified for use on the basis of having anexcellent garment care profile. Garment care profile testing is wellknown in the art and involves testing a composition to be qualifiedusing a wide range of garment or fabric article components, includingfabrics, threads and elastics used in seams, etc., and a range ofbuttons. Preferred fabric article treatment compositions for use hereinhave an excellent garment care profile, for example they have a goodshrinkage or fabric puckering profile.

[0041] A. Polar Solvent

[0042] The polar solvents according to the present invention exhibit atleast one of the following Hansen solubility parameters:

[0043] a fractional polar value (f_(P)) of greater than 0.02 and/orgreater than 0.05; and/or

[0044] a fractional hydrogen bonding value (f_(H)) of greater than 0.10and/or greater than 0.2.

[0045] Nonlimiting examples of polar solvents suitable for use in thefabric article treatment composition of the present invention include:water, alcohols, glycols, polyglycols, ethers, carbonates, dibasicesters, ketones, other oxygenated solvents, and mixtures thereof.Further examples of alcohols include: C1-C126 alcohols, such aspropanol, ethanol, isopropyl alcohol, etc . . . , benzyl alcohol, anddiols such as 1,2-hexanediol. The Dowanol series by Dow Chemical areexamples of glycols and polyglycols useful in the present invention,such as Dowanol TPM, TPnP, DPNB, DPnP, TPnB, PPh, DPM, DPMA, DB, andothers. Further examples include propylene glycol, butylene glycol,polybutylene glycol and more hydrophobic glycols. Examples of carbonatesolvents are ethylene, propylene and butylene carbonates such as thoseavailable under the Jeffsol tradename. Polar solvents for the presentinvention can be further identified through their dispersive (δ_(D)),polar (δ_(P)) and hydrogen bonding (δ_(H)) Hansen solubility parameters.Preferred polar solvents or polar solvent mixtures have fractional polar(f_(P)) and fractional hydrogen bonding (f_(H)) values of f_(P)>0.02 andf_(H)>0.10, where f_(P)=δ_(P)/(δ_(D)+δ_(P)δ_(H)) andf_(H)=δ_(H)/(δ_(D)+δ_(P)+δ_(H)), more preferably f_(P)>0.05 andf_(H>)0.20, and most preferably f_(P)>0.07 and f_(H)>0.30.

[0046] In one embodiment, the polar solvent is selected from the groupconsisting of: water, alcohols, glycols, polyglycols, ethers,carbonates, esters, ketones, other oxygenated solvents, amines, amides,ureas, alkanolamines, alkanolamides phosphate esters, alkyl nitriles andmixtures thereof.

[0047] In one embodiment, the polar solvent comprises from about 0% toabout 50% and/or from about 0.01 to about 20% by weight of water

[0048] B. Hydrophobic Surfactant

[0049] “Hydrophobic surfactant” conventionally refers to materials thatare surface-active either in the water, the lipophilic fluid, or amixture of the two. Some illustrative surfactants include nonionic,cationic and silicone surfactants as used in conventional aqueousdetergent systems.

[0050] Suitable nonionic surfactants include, but are not limited to:

[0051] a) Polyethylene oxide condensates of nonyl phenol and myristylalcohol, such as in U.S. Pat. No. 4,685,930 Kasprzak; and

[0052] b) fatty alcohol ethoxylates, R—(OCH₂CH₂)_(a)OH a=1 to 100,typically 1240, R=hydrocarbon residue 8 to 20 C atoms, typically linearalkyl. Examples polyoxyethylene lauryl ether, with 4 or 23 oxyethylenegroups; polyoxyethylene cetyl ether with 2, 10 or 20 oxyethylene groups;polyoxyethylene stearyl ether, with 2, 10, 20, 21 or 100 oxyethylenegroups; polyoxyethylene (2), (10) oleyl ether, with 2 or 10 oxyethylenegroups. Commercially available examples include, but are not limited to:ALFONIC, BRIJ, GENAPOL, NEODOL, SURFONIC, TRYCOL. See also U.S. Pat. No.6,013,683 Hill et al.,.

[0053] Suitable cationic surfactants include, but are not limited todialkyldimethylammonium salts having the formula:

R′R″N⁺(CH₃)₂X⁻

[0054] where each R′R″ is independently selected from the groupconsisting of 12-30 C atoms or derived from tallow, coconut oil or soy,X=Cl or Br, Examples include: didodecyldimethylammonium bromide (DDAB),dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammoniumbromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethylammonium chloride, didocosyldimethyl ammonium chloride,dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium bromide(DTAB). Commercially available examples include, but are not limited to:ADOGEN, ARQUAD, TOMAH, VARIQUAT. See also U.S. Pat. No. 6,013,683 Hillet al.

[0055] Nonlimiting examples of hydrophobic surfactants suitable for usein the present invention include structure having the following generalformulas:

Y_(u)-(L_(t)-X_(v))_(x)—Y′_(w)  (I)

L_(y)-(X_(v)—Y_(u))_(x)-L′_(z)  (II)

[0056] and mixtures thereof;

[0057] wherein L and L′ are solvent compatibilizing (or lipophilic)moieties, which are independently selected from:

[0058] (a) C1-C22 alkyl or C4-C12 alkoxy, linear or branched, cyclic oracyclic, saturated or unsaturated, substituted or unsubstituted;

[0059] (b) siloxanes having the formula:

M_(a)D_(b)D′_(c)D″_(d)

[0060]  wherein a is 0-2; b is 0-1000; c is 0-50; d is 0-50, providedthat a+c+d is at least 1;

[0061] M is R¹ _(3-e)X_(e)SiO_(1/2) wherein R¹ is independently H, or analkyl group, X is hydroxyl group, and e is 0 or 1;

[0062] D is R⁴ ₂SiO_(2/2), wherein R⁴ is independently H or an alkylgroup;

[0063] D′ is R⁵ ₂SiO_(2/2) wherein R⁵ is independently H, an alkyl groupor (CH₂)_(f)(C₆Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)(C_(k)H_(2k))_(j)—R³,provided that at least one R⁵ is(CH₂)_(f)(C₆Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)(C_(k)H_(2k))_(j)—R³,wherein R³ is independently H, an alkyl group or an alkoxy group, f is1-10, g is 0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C₆Q₄ isunsubstituted or substituted; Q is independently selected from H, C₁₋₁₀alkyl, C₂₋₁₀ alkenyl, and mixtures thereof; and

[0064] D″ is R⁶ ₂SiO_(2/2) wherein R⁶ is independently H, an alkyl groupor (CH₂)_(l)(C₆Q₄)_(m)(A)_(n)-[(T)_(o)-(A′)_(p)-]_(q)-(T′)_(r)Z(G)_(s),wherein I is 1-10; m is 0 or 1; n is 0-5; o is 0-3; p is 0 or 1; q is0-10; r is 0-3; s is 0-3; C₆Q₄ is unsubstituted or substituted; Q isindependently selected from H, C₁₋₁₀ alkyl, C₂₋₁₀ alkenyl, and mixturesthereof; A and A′ are each independently a linking moiety representingan ester, a keto, an ether, a thio, an amido, an amino, a C₁₋₄fluoroalkyl, a C₁₋₄ fluoroalkenyl, a branched or straight chainedpolyalkylene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium, andmixtures thereof; T and T′ are each independently a C₁₋₃₀ straightchained or branched alkyl or alkenyl or an aryl which is unsubstitutedor substituted; Z is a hydrogen, carboxylic acid, a hydroxy, aphosphato, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, abranched or straight-chained polyalkylene oxide, a nitryl, a glyceryl,an aryl unsubstituted or substituted with a C₁₋₃₀ alkyl or alkenyl, acarbohydrate unsubstituted or substituted with a C₁₋₁₀ alkyl or alkenylor an ammonium; G is an anion or cation such as H⁺, Na⁺, Li⁺, K⁺, NH₄ ⁺,Ca⁺², Mg⁺², Cl⁻, Br⁻, I⁻, mesylate or tosylate; and D″ can be cappedwith C₁-C₄ alkyl or hydroxy groups;

[0065] Y and Y′ are hydrophilic moieties, which are independentlyselected from hydroxy; polyhydroxy; C1-C3 alkoxy; mono- ordi-alkanolamine; C1-C4 alkyl substituted alkanolamine; substitutedheterocyclic containing O, S, N; sulfates; carboxylate; carbonate; andwhen Y and/or Y′ is ethoxy (EO) or propoxy (PO), it must be capped withR, which is selected from the group consisting of:

[0066] (i) a 4 to 8 membered, substituted or unsubstituted, heterocyclicring containing from 1 to 3 hetero atoms; and

[0067] (ii) linear or branched, saturated or unsaturated, substituted orunsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbonradicals having from about 1 to about 30 carbon atoms;

[0068] X is a bridging linkage selected from 0; S; N; P; C1 to C22alkyl, linear or branched, saturated or unsaturated, substituted orunsubstituted, cyclic or acyclic, aliphatic or aromatic, interrupted byO, S, N, P; glycidyl, ester, amido, amino, PO₄ ²⁻, HPO₄ ⁻, PO₃ ²⁻, HPO₃⁻, which are protonated or unprotonated;

[0069] u and w are integers independently selected from 0 to 20,provided that u+w>1;

[0070] t is an integer from 1 to 10;

[0071] v is an integer from 0 to 10;

[0072] x is an integer from 1 to 20; and

[0073] y and z are integers independently selected from 1 to 10.

[0074] Nonlimiting examples of surfactants having the above formulainclude:

[0075] (1) alkanolamines/alkanolamides;

[0076] (2) phophate/phosphonate esters;

[0077] (3) gemini surfactants including, but are not limited to, geminidiols, gemini amide alkoxylates, gemini amino alkoxylates;

[0078] (4) capped nonionic surfactants;

[0079] (5) capped silicone surfactants such as nonionic siliconeethoxylates, silicone amine derivatives;

[0080] (6) alkyl alkoxylates;

[0081] (7) polyol surfactants; and

[0082] (8) mixtures thereof.

[0083] Another class of surfactants can include siloxane-basedsurfactants. The siloxane-based surfactants in this application may besiloxane polymers for other applications. The siloxane-based surfactantstypically have a weight average molecular weight from 500 to 20,000daltons. Such materials, derived from poly(dimethylsiloxane), are wellknown in the art. In the present invention, not all such siloxane-basedsurfactants are suitable, because they do not provide improved cleaningof soils compared to the level of cleaning provided by the lipophilicfluid itself.

[0084] Suitable siloxane-based surfactants comprise a polyether siloxanehaving the formula:

M_(a)D_(b)D′_(c)D″_(d)M′_(2-a)

[0085] wherein a is 0-2; b is 0-1000; c is 0-50; d is 0-50, providedthat a+c+d is at least 1;

[0086] M is R¹ _(3-e)X_(e)SiO_(1/2) wherein R¹ is independently H or analkyl group, X is hydroxyl group, and e is 0 or 1;

[0087] M′ is R² ₃SiO_(1/2) wherein R² is independently H, an alkylgroup, or(CH₂)_(f)(C₆Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆₀)_(i)(C_(k)H_(2k))_(j)—R³,provided that at least one R² is(CH₂)_(f)(C6Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆O)_(i)(C_(k)H_(2k))_(j)—R³,wherein R³ is independently H, an alkyl group or an alkoxy group, f is1-10, g is 0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C₆Q₄ isunsubstituted or substituted; Q is independently selected from H, C₁₋₁₀alkyl, C₁₋₁₀ alkenyl, and mixtures thereof;

[0088] D is R⁴ ₂SiO_(2/2), wherein R⁴ is independently H or an alkylgroup;

[0089] D′ is R⁵ ₂SiO_(2/2) wherein R⁵ is independently H, an alkylgroup, or(CH₂)_(f)(C₆Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆₀)_(i)(C_(k)H_(2k))_(j)—R³,provided that at least one R⁵ is(CH₂)_(f)(C6Q₄)_(g)O—(C₂H₄O)_(h)—(C₃H₆₀)_(i)(C_(k)H_(2k))_(j)—R³,wherein R³ is independently H, an alkyl group or an alkoxy group, f is1-10, g is 0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C₆Q₄ isunsubstituted or substituted; Q is independently selected from H, C₁₋₁₀alkyl, C₁₋₁₀ alkenyl, and mixtures thereof; and

[0090] D″ is R⁶ ₂SiO_(2/2) wherein R⁶ is independently H, an alkyl groupor (CH₂)_(l)(C₆Q₄)_(m)(A)_(n)-[(T)_(o)-(A′)_(p)-]_(q)-(T′)_(r)Z(G)_(s),wherein I is 1-10; m is 0 or 1; n is 0-5; o is 0-3; p is 0 or 1; q is0-10; r is 0-3; s is 0-3; C₆Q₄ is unsubstituted or substituted; Q isindependently selected from H, C₁₋₁₀ alkyl, C₁₋₁₀ alkenyl, and mixturesthereof; A and A′ are each independently a linking moiety representingan ester, a keto, an ether, a thio, an amido, an amino, a C₁₋₄fluoroalkyl, a C₁₋₄ fluoroalkenyl, a branched or straight chainedpolyalkylene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium, andmixtures thereof; T and T′ are each independently a C₁₋₃₀ straightchained or branched alkyl or alkenyl or an aryl which is unsubstitutedor substituted; Z is a hydrogen, carboxylic acid, a hydroxy, aphosphato, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, abranched or straight-chained polyalkylene oxide, a nitryl, a glyceryl,an aryl unsubstituted or substituted with a C₁₋₃₀ alkyl or alkenyl, acarbohydrate unsubstituted or substituted with a C₁₋₁₀ alkyl or alkenylor an ammonium; G is an anion or cation such as H⁺, Na⁺, Li⁺, K⁺, NH₄ ⁺,Ca⁺², Mg⁺², Cl⁻, Br⁻, I⁻, mesylate or tosylate.

[0091] Examples of the types of siloxane-based surfactants describedherein above may be found in EP-1,043,443A1, EP-1,041,189 andWO-01/34,706 (all to GE Silicones) and U.S. Pat. No. 5,676,705, U.S.Pat. No. 5,683,977, U.S. Pat. No. 5,683,473, and EP-1,092,803A1 (allassigned to Lever Brothers).

[0092] Nonlimiting commercially available examples of suitablesiloxane-based surfactants are TSF 4446 (ex. General ElectricSilicones), XS69-B5476 (ex. General Electric Silicones); Jenamine HSX(ex. DelCon) and Y12147 (ex. OSi Specialties).

[0093] Yet another class of materials suitable for the surfactantcomponent is organic in nature. Preferred materials areorganosulfosuccinate surfactants, with carbon chains of from about 6 toabout 20 carbon atoms. Most preferred are organosulfosuccinatescontaining dialkly chains, each with carbon chains of from about 6 toabout 20 carbon atoms. Also preferred are chains containing aryl oralkyl aryl, substituted or unsubstituted, branched or linear, saturatedor unsaturated groups. Nonlimiting commercially available examples ofsuitable organosulfosuccinate surfactants are available under the tradenames of Aerosol OT and Aerosol TR-70 (ex. Cytec).

[0094] Suitable silicone surfactants include, but are not limited to thepolyalkyleneoxide polysiloxanes having a dimethyl polysiloxanehydrophobic moiety and one or more hydrophilic polyalkylene side chainsand have the general formula:

R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R¹)SiO]_(b)—Si(CH₃)₂—R¹

[0095] wherein a+b are from about 1 to about 50, preferably from about 3to about 30, more preferably from about 10 to about 25, and each R¹ isthe same or different and is selected from the group consisting ofmethyl and a poly(ethyleneoxide/propyleneoxide) copolymer group havingthe general formula:

—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R²

[0096] with at least one R¹ being a poly(ethyleneoxide/propyleneoxide)copolymer group, and wherein n is 3 or 4, preferably 3; total c (for allpolyalkyleneoxy side groups) has a value of from 1 to about 100,preferably from about 6 to about 100; total d is from 0 to about 14,preferably from 0 to about 3; and more preferably d is 0; total c+d hasa value of from about 5 to about 150, preferably from about 9 to about100 and each R² is the same or different and is selected from the groupconsisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and anacetyl group, preferably hydrogen and methyl group. Examples of thesesurfactants may be found in U.S. Pat. No. 5,705,562 Hill and U.S. Pat.No. 5,707,613 Hill, both of which are incorporated herein by reference.

[0097] Examples of this type of surfactants are the Silwet® surfactantswhich are available CK Witco, OSi Division, Danbury, Conn.Representative Silwet® surfactants are as follows. Name Average MWAverage a + b Average total c L-7608 600 1 9 L-7607 1,000 2 17 L-77 6001 9 L-7605 6,000 20 99 L-7604 4,000 21 53 L-7600 4,000 11 68 L-76575,000 20 76 L-7602 3,000 20 29

[0098] The molecular weight of the polyalkyleneoxy group (R¹) is lessthan or equal to about 10,000. Preferably, the molecular weight of thepolyalkyleneoxy group is less than or equal to about 8,000, and mostpreferably ranges from about 300 to about 5,000. Thus, the values of cand d can be those numbers which provide molecular weights within theseranges. However, the number of ethyleneoxy units (C₂H₄O) in thepolyether chain (R¹) must be sufficient to render the polyalkyleneoxidepolysiloxane water dispersible or water soluble. If propyleneoxy groupsare present in the polyalkylenoxy chain, they can be distributedrandomly in the chain or exist as blocks. Preferred Silwet® surfactantsare L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.Besides surface activity, polyalkyleneoxide polysiloxane surfactants canalso provide other benefits, such as antistatic benefits, and softnessto fabric articles.

[0099] The preparation of polyalkyleneoxide polysiloxanes is well knownin the art. Polyalkyleneoxide polysiloxanes of the present invention canbe prepared according to the procedure set forth in U.S. Pat. No.3,299,112.

[0100] Another suitable silicone surfactant is SF-1488, which isavailable from GE silicone fluids.

[0101] These and other surfactants suitable for use in combination withthe lipophilic fluid as adjuncts are well known in the art, beingdescribed in more detail in Kirk Othmer's Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants and DetersiveSystems”. Further suitable nonionic detergent surfactants are generallydisclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30,1975, at column 13, line 14 through column 16, line 6.

[0102] In one embodiment, the hydrophobic surfactant exhibits an HLBvalue of from about 0.1 to about 12 and/or from about 3 to about 9.

[0103] In another embodiment, the hydrophobic surfactant is selectedfrom the group consisting of: silicone-based surfactants,organosulfosuccinate surfactants, alkanolamines, alkanolamides, alcoholalkoxylates, gemini surfactants, polyhydroxy fatty acid amides,alkylhydrogen phosphates and salts thereof, saccharide derivatives andAlkanolamine based surfactants have the ability to aid in cleaning forwater soluble and water based soils. However, these functionalitiestypically do not have good compatibility in dry cleaning solvent such asdecamethylcyclopentasiloxane.

[0104] Suitable alkanolamine surfactant would have the general formula(I) wherein the H moiety is an alkanolamine moiety having the followingformula:

[0105] wherein R¹, R², R³ are same or different and are independentlyselected from H, hydrocarbons, polyoxyalkylenes, siloxanes orflurorinated groups; and at least one hydroxyl group is present in thealkanolamine moiety, either to terminate one or more R groups or bepresent within one or more of the R groups as a secondary hydroxylgroup. Hydrocarbon groups may be linear or branched, cyclic or acyclic,saturated or unsaturated, and contain about 1-30 carbons, preferablyabout 6 to 30 carbons, more preferably about 8 to 18 carbons. Siliconeand fluorinated groups may consist of 1-50 repeat units.

[0106] The method of functionalizing the alkanolamine moiety may be, butnot limited to alkylation, esterification, etherification, amidation,amination and other linking chemistries. Thus, the correspondingbridging group B_(j) can be alkyl, ester, ether, amido, and aminolinking groups. The number and size of the solvotrope groups S_(k) usedfor a given alkanolamine group is important for optimized performance.When a surfactant contains too numerous and/or too large solvotropegroups, the surfactants may exhibit too high a solubility profile in thesolvent or too high a molecular weight, both of which lead toineffective cleaning and/or soil removal performance. Moreover, thesurfactant may become a solid, which makes solubiliztion in the solventand formulation difficulty. On the other hand, when the surfactantcontains too few and/or too small solvotrope groups, the surfactant mayexhibit poor solubility in the solvent and reduce the effectiveness ofthe alkanolamine moiety in cleaning and/or soil removal.

[0107] The present invention alkanolamine based surfactants may compriseone or more polyalkylene oxide units or solvatrope groups, S within thesurfactant structure. The alkoxy moieties are selected from ethoxy (EO),propoxy (PO), butoxy (BO), higher alkoxy moieties, and mixtures thereof,such as mixed EO/PO, EO/B, PO/BO, EO/PO/BO, and the like, wherein thenumber of repeat units (m) may be 1 to 50. The alkoxy moieties may beeither a distribution having an average degree of alkoxylation of mrepeat units, or a monodispersed moiety with m repeat units ofalkoxylation

[0108] In one embodiment of the present invention, the functionalizedalkanolamine moiety has an average of at least 1 solvotrope moiety persurfactant molecule. Preferably, the surfactant molecules containssufficient number of solvotrope moieties to rpovide solventcompatibility. In another embodiment of the invention, the alkanolaminemoiety has an average of at least 2 solvent compatibility groups peralkanolamine moiety (i.e., a moiety having a “twin tail” structure). Thesolvotrope moiety can be selected from OH, alkoxy, and mixtures thereof.

[0109] The following are nonlimiting examples of functionalizedalkanolamine containing surfactants useful in the present invention:

[0110] The alkanolamine based surfactants of the present invention haveat least 1 free hydroxyl per molecule.

[0111] In some embodiments, the composition comprises from about 0.01 toabout 10 wt % of an alkanolamine based surfactant, from about 0 to about20 wt % of water, from about 0.1 to about 20 wt % of other detergentadjuncts, and the balance of lipophilic fluids. These cleaningcompositions have been shown to enhance the overall cleaning and stainremoval performance of the composition. These compositions areparticularly effective in the cleaning and removing stains of blood,grass and clay.

[0112] Phosphate/phosphonate ether surfactants have the general formula(I) wherein the B moiety can be a phosphate based moiety having thefollowing formula:

[0113] wherein R¹, R², R³ are independently selected from H, OR⁴, C₁-C₂₂alkyl, which are linear or branched, substituted or unsubstituted,cyclic or acyclic, and optionally interrupted by O, N, S, or P; R⁴ isselected from:

[0114] H, Na, K, L₁, C₁-C₂₂ alkyl, which are linear or branched,substituted or unsubstituted, cyclic or acyclic, and optionallyinterrupted by O, N, S, or P; R⁵ is selected from H, CH₃, C₂H₅, C₃H₇,C₄H₉; and n is an integer from 0 to 10.

[0115] The following are nonlimiting examples of functionalizedphosphate ester containing surfactants useful in the present invention:

[0116] In some embodiments, the composition comprises from about 0.01 toabout 10 wt % of a phosphate based surfactant, from about 0 to about 20wt % of water, from about 0.1 to about 20 wt % of other detergentadjuncts, and the balance of lipophilic fluids. These cleaningcompositions have been shown to enhance the overall cleaning and stainremoval performance of the composition. These compositions areparticularly effective in the cleaning and removing stains of blood,grass and tea.

[0117] Whereas the conventional surfactants generally have onehydrophilic group and one hydrophobic group, the Gemini surfactants arecompounds having at least two hydrophobic groups and at least twohydrophilic groups. See J. American Chemical Soc., 115, 10083-10090(1993); and Chemtech, March 1993, pp 30-33. Gemini surfactants have beenfound to be very effective emulsifiers when used at very lowconcentrations in comparison to conventional surfactants. Thischaracteristic further leads to superior detergency at very lowconcentrations.

[0118] The following are nonlimiting examples of Gemini surfactantssuitable for use in the present invention:

[0119] In some embodiments, the composition comprises from about 0.01 toabout 10 wt % of a gemini surfactant, from about 0 to about 20 wt % ofwater, from about 0.1 to about 20 wt % of other detergent adjuncts, andthe balance of lipophilic fluids. These cleaning compositions have beenshown to enhance the overall cleaning and stain removal performance ofthe composition. These compositions are particularly effective in thecleaning and removing clays and make-up stains.

[0120] In one embodiment of the present invention, a capped nonionicsurfactant according to formula (i) can have the general formula:

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)O_(n)R²

[0121] wherein R¹ and R² are linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon radicals having fromabout 1 to about 30 carbon atoms; R³ is H, or a linear aliphatichydrocarbon radical having from about 1 to about 4 carbon atoms; x is aninteger having an average value from 1 to about 40, wherein when x is 2or greater, R³ may be the same or different and k and j are integershaving an average value of from about 1 to about 12, and more preferably1 to about 5, n is an integer from 0 to 1; further wherein when x is 15or greater and R³ is H and methyl, at least four of R³ are methyl,further wherein when x is 15 or greater and R³ includes H and from 1 to3 methyl groups, then at least one R³ is ethyl, propyl or butyl, furtherwherein R² can optionally be alkoxylated, wherein said alkoxy isselected from ethoxy, propoxy, butyloxy and mixtures thereof; wherein R¹and R² are preferably linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from about 6 to about22 carbon atoms with about 8 to about 18 carbon atoms being mostpreferred. R² can optionally be alkoxylated, wherein the alkoxy isselected from ethoxy, propoxy, butyloxy and mixtures thereof. H or alinear aliphatic hydrocarbon radical having from about 1 to about 2carbon atoms is most preferred for R³. Preferably, x is an integerhaving an average value of from about 1 to about 20, more preferablyfrom about 6 to about 15. Also, preferred in the present invention arealcohol surfactants.

[0122] In another embodiment of the present invention, the cappednonionic surfactant according to formula (i) can be an ether-cappedpoly(oxyalkylated) alcohol surfactant, specifically, with the formula:

RO(R¹O)_(x)CH(CH₃)OR²

[0123] wherein, R is selected from the group consisting of linear orbranched, saturated or unsaturated, substituted or unsubstituted,aliphatic or aromatic hydrocarbon radicals having from about 1 to about30 carbon atoms; R¹ may be the same or different, and is independentlyselected from the group consisting of branched or linear C₂ to C₇alkylene in any given molecule; x is a number from 1 to about 30; and R²is selected from the group consisting of:

[0124] (iii) a 4 to 8 membered substituted, or unsubstitutedheterocyclic ring containing from 1 to 3 hetero atoms; and

[0125] (iv) linear or branched, saturated or unsaturated, substituted orunsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbonradicals having from about 1 to about 30 carbon atoms;

[0126] provided that when R² is (ii) then either: (A) at least one of R¹is other than C₂ to C₃ alkylene; or (B) R² has from 6 to 30 carbonatoms, and with the further proviso that when R² has from 8 to 18 carbonatoms, R is other than C₁ to C₅ alkyl.

[0127] In yet another embodiment of the present invention, the cappednonionic surfactant according to formula (i) can be an ether-cappedpoly(oxyalkylated) alcohols having the formula:

RO(R¹O)_(n)R²

[0128] In one aspect of the present invention R is a linear or branched,saturated or unsaturated, substituted or unsubstituted, aliphatichydrocarbon radical having from about 1 to about 20 carbon atoms, evenmore preferably R is a linear or branched, saturated, aliphatichydrocarbon radicals having from about 4 to about 18 carbon atoms.

[0129] In one aspect of the present invention R, R¹ and R² are selectedsuch that the ether-capped poly(oxyalkylated) alcohol surfactantcontains one or more chiral carbon atoms.

[0130] In one aspect of the present invention, R is a hydrocarbonradical of the formula:

[0131] wherein R⁴, R⁵, and R⁶ are each independently selected fromhydrogen, and C₁-C₃ alkyl, more preferably hydrogen, C₁-C₂ alkyl, evenmore preferably hydrogen, and methyl, provided that R⁴, R⁵, and R⁶ arenot all hydrogen and, when t is 0, at least R⁴ or R⁵ is not hydrogen; q,r, s, t are each independently integers from 0 to 13. In one morepreferred form of this aspect R is selected from the formulas:

[0132] wherein n, m, j and k are each independently integers from 0 to13.

[0133] In one aspect of the present invention R² is a hydrocarbonradical of the formula:

—C(CH₃)₂R³

[0134] R³ is selected from the group consisting of linear or branched,saturated or unsaturated, substituted or unsubstituted, aliphatic oraromatic hydrocarbon radicals having from about 1 to about 30, morepreferably 1 to 20, even more preferably 1 to 15, carbon atoms, providedthat when R³ is methyl, R is branched. In one embodiment of this aspectof the present invention, R³ is ethyl.

[0135] In one aspect of the present invention R² is a 4 to 8 memberedsubstituted, or unsubstituted heterocyclic ring containing from 1 to 3hetero atoms. In one embodiment of this aspect of the invention thehetero atoms are selected from the group comprising oxygen, nitrogen,sulfur and mixtures thereof. In one embodiment of this aspect of theinvention R² is a 5 or 6 member heterocycle. In another embodiment ofthis aspect of the present invention R² is selected from the groupconsisting of:

[0136] wherein each R⁷ is independently selected from the groupconsisting of hydrogen, linear or branched, saturated or unsaturated,substituted or unsubstituted, aliphatic hydrocarbon or alkoxy radicalhaving from about 1 to about 10 carbon atoms, or R⁷ is a saturated orunsaturated, substituted or unsubstituted, alicyclic or aromatichydrocarbon radical having, from about 1 to about 10 carbon atoms, whichis fused to the heterocyclic ring; each A is independently selected fromthe group consisting of O, and N(R⁸)_(a), wherein R⁸ is independentlyselected from the group consisting of hydrogen, linear or branched,saturated or unsaturated, substituted or unsubstituted, aliphatichydrocarbon radical having from about 1 to about 10 carbon atoms, and ais either 0 or 1; z is an integer from 1 to 3.

[0137] In another embodiment of this aspect of the present invention R²is selected from the group consisting of:

[0138] wherein R⁷ is defined as above.

[0139] The following are nonlimiting examples of capped nonionicsurfactants suitable for use in the present invention:

[0140] In some embodiments, the composition comprises from about 0.01 toabout 10 wt % of a capped nonionic surfactant, from about 0 to about 20wt % of water, from about 0.1 to about 20 wt % of other detergentadjuncts, and the balance of lipophilic fluids. These cleaningcompositions have been shown to enhance the overall cleaning and stainremoval performance of the composition. These compositions areparticularly effective in the cleaning and removing stains of grass andclay.

[0141] In one embodiment of the present invention, the amide containingsurfactant has a structure according to formula (i) or (ii) below:

[0142] R=C₁-C₂₂ linear alkyl, alkyl substituted aromatic, C₃-C₂₂branched alkyl, linear alkenyl, branched alkenyl, C₅-C₂₂ cyclic alkyl,cyclic alkenyl, aryl

[0143] L=C₁-C₁₂ substituted/unsubstituted alkyl, alkyl substitutedaromatic, C₃-C₁₂ branched alkyl, linear alkenyl, branched alkenyl,C₅-C₁₂ cyclic alkyl, cyclic alkenyl, aryl

[0144] or −[(CR₂R₃)_(k)—X]_(m)—(CR₄R₅)_(n)—; where R₂,R₃,R₄,R₅═H, alkyl,X=O, N, k=2-6, m=0-5 & n=2-6

[0145] A=H, —(R₆O)_(n)R₇; where R₆═C₂-C₄ alkylene and R₇═H or R mixturesthereof.

[0146] Another class of materials can include polyol-based surfactants.“Polyol”, as used herein, means any aliphatic or aromatic compoundcontaining at least two free hydroxyl groups. In practicing theprocesses disclosed herein, the selection of a suitable polyol is simplya matter of choice. For example, suitable polyols may be selected fromthe following classes: saturated and unsaturated straight and branchedchain linear aliphatic; saturated and unsaturated cyclic aliphatic,including heterocyclic aliphatic; or mononuclear or polynucleararomatics, including heterocyclic aromatics. Carbohydrates and glycolsare exemplary polyols. Especially preferred glycols include glycerin.Monosaccharides suitable for use herein include, for example, mannose,galactose, arabinose, xylose, ribose, apiose, rhamnose, psicose,fructose, sorbose, tagitose, ribulose, xylulose, and erythrulose.Oligosaccharides suitable for use herein include, for example, maltose,kojibiose, nigerose, cellobiose, lactose, melibiose, gentiobiose,turanose, rutinose, trehalose, sucrose and raffinose. Polysaccharidessuitable for use herein include, for example, amylose, glycogen,cellulose, chitin, inulin, agarose, zylans, mannan and galactans.Although sugar alcohols are not carbohydrates in a strict sense, thenaturally occurring sugar alcohols are so closely related to thecarbohydrates that they are also preferred for use herein. The sugaralcohols most widely distributed in nature and suitable for use hereinare sorbitol, mannitol and galactitol. Other polyols includepentaerythritol and derivatives thereof.

[0147] Particular classes of materials suitable for use herein includemonosaccharides, disaccharides and sugar alcohols. Other classes ofmaterials include sugar ethers, alkoxylated polyols, such as polyethoxyglycerol and other polyols containing amines such as glucosamine. Polyolbased surfactants have the ability to aid in cleaning for water solubleand water based soils. However, these functionalities typically do nothave good compatibility in dry cleaning solvent such asdecamethylcyclopentasiloxane. The present invention utilizes a solventcompatibility group functionalized onto a polyol for improved cleaning.

[0148] Example of a general sucrose based structure is shown in thefollowing structure:

[0149] where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ can be any combinationof H, hydrocarbon, polyoxyalkylene, siloxane or flurorinated groups.Hydrocarbon groups may consist of 1-30 carbons that may be linear,cyclic, branched, saturated or unsaturated. Silicone and fluorinatedgroups may consist of 1-50 repeat units. R substitution on the polyolmay be a distribution with an average degree of substitution when totalsubstitution is not complete. The number and size of the solventcompatible groups used for a given polyol is important for optimizedperformance. Too large and/or too many solvent compatibility groups canlead to various unwanted properties such as too high a solubilityprofile in the solvent, too high a molecular weight leading to moleculeinefficiency and potentially the materials becoming a solid makingsolubiliztion in the solvent and formulation difficulty. Too few and/ortoo small solvent compatible groups can lead to reduced performance ofthe polyol due to poor solubility in the solvent.

[0150] The present invention polyol based surfactants may comprise oneor more polyalkylene oxide units within the structure. EO/PO/BO andhigher materials are alkoxy moieties, preferably selected from ethoxy,propoxy, butoxy and mixed EO/PO, EO/BO. PO/BO, EO/PO/BO groups whereinthe number of repeat units (m) may consist of 1-50 units. The alkoxymoieties may be either a distribution or with an average degree ofalkoxylation being corresponding to m or it may be a single specificchain with an alkoxylation number exactly corresponding to m. Placementof the alkoxy moieties in the stucture may be near the polyol moiety oron the ends on the R units.

[0151] The following general example of ethoxylated sucrose is shownbelow:

[0152] R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ can be any combination of H,hydrocarbon, polyoxyalkylene, siloxane or flurorinated groups. Themethod of functionalizing the polyol may be, but not limited toesterification, etherification, amidation and other linking chemistries.

[0153] In one embodiment of the present invention, the functionalizedpolyol has an average of at least 1 solvent compatibility group permolecule. In another embodiment of the invention, the polyol has anaverage of at least 2 solvent compatibility groups per molecule (twintail), while in another embodiment the polyol has an average of fromabout 3 to about 8 solvent compatibility groups per molecule.

[0154] In one embodiment of the present invention, the functionalizedpolyol has an average of at least 20H groups per molecule. In anotherembodiment of the invention, the polyol has an average of at least 30Hgroups per molecule, while in another embodiment the polyol has anaverage of from about 3 to about 80H groups per molecule.

[0155] In one embodiment of the present invention, the functionalizedpolyol may have the 2 or more hydroxyls replaced with 1 or more of thefollowing groups or combinations of groups: sulfate, sulfonate,carboxylate, amine, alkanolamine, phosphate and amide containingmoieties. The polyol may be transesterified for example withmethyloleate on several of the hydroxyl groups. The oleate esters of thepolyol then become “capping” groups.

[0156] The following structures exemplify polyol containing surfactantsuseful in the present invention:

[0157] Sucrose ester from soybean oil (mainly oleyl). Solventcompatibility groups a distribution across hydroxyls and above structurea representation only.

[0158] The polyol based surfactants of the present invention have atleast 2 free hydroxyls per molecule, more preferably higher as long assolvent compatibility is maintained.

[0159] The polyol based surfactants of the present invention have atleast one compatibility group per molecule, more preferably the minimumnumber needed to maintain solvent compatibility.

[0160] The polyol based surfactants of the present invention have Rgroups which are unsaturated or branched hydrocarbons ranging from 6 to30 total carbons, more preferably from 8 to 18 carbons.

[0161] The polyol based surfactants are present in the cleaningformulations of the present invention at levels from 0.001% to 10%, morepreferably from about 0.01% to 2%.

[0162] In one embodiment, the hydrophobic surfactant comprises one ormore of the following structures:

[0163] Optional Ingredients

[0164] Carrier Solvents

[0165] “Carrier solvents” as used herein means a solvent that isselected from the group consisting of: silicone solvents,hydrofluoroether solvents, perfluorinated solvents, hydrocarbonsolvents, halogenated hydrocarbons, and mixtures thereof.

[0166] Cleaning Adjuncts

[0167] The compositions of the present invention may optionally compriseat least one cleaning adjunct. The cleaning adjuncts can vary widely andcan be used at widely ranging levels. For example, detersive enzymessuch as proteases, amylases, cellulases, lipases and the like as well asbleach catalysts including the macrocyclic types having manganese orsimilar transition metals all useful in laundry and cleaning productscan be used herein at very low, or less commonly, higher levels.Cleaning adjuncts that are catalytic, for example enzymes, can be usedin “forward” or “reverse” modes, a discovery independently useful fromthe fabric treating methods of the present invention. For example, alipolase or other hydrolase may be used, optionally in the presence ofalcohols as cleaning adjuncts, to convert fatty acids to esters, therebyincreasing their solubility in the lipophilic fluid. This is a “reverse”operation, in contrast with the normal use of this hydrolase in water toconvert a less water-soluble fatty ester to a more water-solublematerial. In any event, any cleaning adjunct must be suitable for use incombination with a lipophilic fluid in accordance with the presentinvention.

[0168] Some suitable cleaning adjuncts include, but are not limited to,builders, surfactants, other than those described above with respect tothe surfactant component, enzymes, bleach activators, bleach catalysts,bleach boosters, bleaches, alkalinity sources, antibacterial agents,colorants, perfumes, pro-perfumes, finishing aids, lime soapdispersants, odor control agents, odor neutralizers, polymeric dyetransfer inhibiting agents, crystal growth inhibitors, photobleaches,heavy metal ion sequestrants, anti-tarnishing agents, anti-microbialagents, anti-oxidants, anti-redeposition agents, polymer dispersants,soil release polymers, electrolytes, pH modifiers, thickeners,abrasives, divalent or trivalent ions, metal ion salts, enzymestabilizers, corrosion inhibitors, diamines or polyamines and/or theiralkoxylates, suds stabilizing polymers, solvents, process aids, fabricsoftening agents, optical brighteners, hydrotropes, suds or foamsuppressors, suds or foam boosters and mixtures thereof.

[0169] Suitable odor control agents, which may optionally be used asfinishing agents, include agents include, cyclodextrins, odorneutralizers, odor blockers and mixtures thereof. Suitable odorneutralizers include aldehydes, flavanoids, metallic salts,water-soluble polymers, zeolites, activated carbon and mixtures thereof.

[0170] Perfumes and perfumery ingredients useful in the compositions ofthe present invention comprise a wide variety of natural and syntheticchemical ingredients, including, but not limited to, aldehydes, ketones,esters, and the like. Also included are various natural extracts andessences which can comprise complex mixtures of ingredients, such asorange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamicessence, sandalwood oil, pine oil, cedar, and the like. Finishedperfumes may comprise extremely complex mixtures of such ingredients.Pro-perfumes are also useful in the present invention. Such materialsare those precursors or mixtures thereof capable of chemically reacting,e.g., by hydrolysis, to release a perfume, and are described in patentsand/or published patent applications to Procter and Gamble, Firmenich,Givaudan and others.

[0171] Bleaches, especially oxygen bleaches, are another type ofcleaning adjunct suitable for use in the compositions of the presentinvention. This is especially the case for the activated and catalyzedforms with such bleach activators as nonanoyloxybenzenesulfonate and/orany of its linear or branched higher or lower homologs, and/ortetraacetylethylenediamine and/or any of its derivatives or derivativesof phthaloylimidoperoxycaproic acid (PAP) or other imido- oramido-substituted bleach activators including the lactam types, or moregenerally any mixture of hydrophilic and/or hydrophobic bleachactivators (especially acyl derivatives including those of the C₆-C₁₆substituted oxybenzenesulfonates).

[0172] Also suitable are organic or inorganic peracids both includingPAP and other than PAP. Suitable organic or inorganic peracids for useherein include, but are not limited to: percarboxylic acids and salts;percarbonic acids and salts; perimidic acids and salts;peroxymonosulfuric acids and salts; persulphates such as monopersulfate;peroxyacids such as diperoxydodecandioic acid (DPDA); magnesiumperoxyphthalic acid; perlauric acid; perbenzoic and alkylperbenzoicacids; and mixtures thereof.

[0173] One class of suitable organic peroxycarboxylic acids has thegeneral formula:

[0174] wherein R is an alkylene or substituted alkylene group containingfrom 1 to about 22 carbon atoms or a phenylene or substituted phenylenegroup, and Y is hydrogen, halogen, alkyl, aryl, —C(O)OH or —C(O)OOH.

[0175] Particularly preferred peracid compounds are those having theformula:

[0176] wherein R is C₁₋₄ alkyl and n is an integer of from 1 to 5. Aparticularly preferred peracid has the formula where R is CH₂ and n is 5i.e., phthaloylamino peroxy caproic acid (PAP) as described in U.S. Pat.Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431. PAP isavailable from Ausimont SpA under the tradename Euroco.

[0177] Hydrogen peroxide is a highly preferred bleaching agent.

[0178] Other cleaning adjuncts suitable for use in the compositions ofthe present invention include, but are not limited to, buildersincluding the insoluble types such as zeolites including zeolites A, Pand the so-called maximum aluminum P as well as the soluble types suchas the phosphates and polyphosphates, any of the hydrous, water-solubleor water-insoluble silicates, 2,2′-oxydisuccinates, tartrate succinates,glycolates, NTA and many other ethercarboxylates or citrates; chelantsincluding EDTA, S,S′-EDDS, DTPA and phosphonates; water-solublepolymers, copolymers and terpolymers; soil release polymers; opticalbrighteners; processing aids such as crisping agents and/fillers;anti-redeposition agents; hydrotropes, such as sodium, or calcium cumenesulfonate, potassium napthalenesulfonate, or the like, humectant; otherperfumes or pro-perfumes; dyes; photobleaches; thickeners; simple salts;alkalis such as those based on sodium or potassium including thehydroxides, carbonates, bicarbonates and sulfates and the like; andcombinations of one or more of these cleaning adjuncts.

[0179] One particularly preferred class of cleaning adjuncts isadditives comprising a strongly polar and/or hydrogen-bonding headgroup, further enhances soil removal by the compositions of the presentinvention. Examples of the strongly polar and/or hydrogen-bonding headgroup are alcohols, carboxylic acids, sulfates, sulphonates, phosphates,phosphonates, and nitrogen containing materials. Preferred additives arenitrogen containing materials selected from the group consisting ofprimary, secondary and tertiary amines, diamines, triamines, ethoxylatedamines, amine oxides, amides, betaines, quaternary ammonium salts, andmixtures thereof. Most highly preferred materials are amino-functionalsiloxanes, having one or more of the following properties: i) at leastabout 60% by weight silicone content; and ii) alkyleneoxy groups, mostpreferably ethyleneoxy groups.

[0180] The compositions of the invention can be formulated as a liquid,a thickened aqueous liquid, a semi-solid or gel, or a solid productform. The thickened liquid product form can be manufactured byincorporation of a thickening agent. Inorganic thickeners typicallycomprise clays, silicates and other well known inorganic thickeners.Organic thickeners include thixotropic and non-thixotropic thickeners.Preferred thickeners have some substantial proportion of watersolubility to promote easy removability. Examples of useful solubleorganic thickeners for the compositions of the invention comprisecarboxylated vinyl polymers such as polyacrylic acids and sodium saltsthereof, ethoxylated cellulose, polyacrylamide thickeners, xanthanthickeners, guargum, sodium alginate and algin by-products, hydroxypropyl cellulose, hydroxy ethyl cellulose and other similar aqueousthickeners that have some substantial proportion of water solubility.

[0181] A hardening agent, as used in the present method andcompositions, is a compound or system of compounds, organic orinorganic, that significantly contributes to the uniform solidificationof the composition. Preferably, the hardening agent is compatible withthe active ingredients of the composition, and is capable of providingan effective amount of hardness to the processed composition. Thehardening agent should also be capable of forming a homogeneous matrixwith the ingredients when mixed and solidified to provide a uniformdissolution of the cleaning agent from the solid composition during use.The amount of hardening agent included in the cleaning composition willvary according to the type of cleaning composition being prepared, theingredients of the composition, the intended use of the composition, thequantity of dispensing solution applied to the solid composition overtime during use, the temperature of the dispensing solution, thehardness of the dispensing solution, the physical size of the solidcomposition, the concentration of the other ingredients, theconcentration of the cleaning agent in the composition, and other likefactors. It is preferred that the amount of the hardening agent iseffective to combine with the cleaning agent and other ingredients ofthe composition to form a homogeneous mixture under continuous mixingconditions and a temperature at or below the melting temperature of thehardening agent. The hardening agent can form a matrix with the cleaningagent and other ingredients which will harden to a solid form underambient Another preferred hardening agent is a polyethylene glycol (PEG)or propylene glycol compound for use in a cleaning compositioncomprising a nonionic surfactant cleaning agent, such as a nonyl phenolethoxylate, a linear alkyl alcohol ethoxylate, an ethyleneoxide/propylene oxide block copolymers such as the surfactants availablecommercially under the trademark PLURONIC® from BASF-Wyandotte. Thesolidification rate of cleaning compositions comprising a polyethyleneglycol hardening agent made according to the invention will vary, atleast in part, according to the amount and the molecular weight of thepolyethylene glycol added to the composition.

[0182] The hardening agent may also be a hydratable substance such as ananhydrous sodium carbonate, anhydrous sodium sulfate, or combinationthereof. A hydratable hardening agent, according to the invention, iscapable of hydrating to bind free water present in a liquid detergentemulsion to the extent that the liquid emulsion becomes hardened orsolidified to a homogenous solid. The amount of a hydratable substanceincluded in a detergent composition processed according to theinvention, will vary according to the percentage of water present in theliquid emulsion as well as the hydration capacity of the otheringredients.

[0183] Other hardening agents that may be used in a cleaning compositionprocessed according to the invention include, for example, urea, alsoknown as carbamide, starches that have been made water-soluble throughan acid or alkaline treatment process, and various inorganics thatimpart solidifying properties to a heated liquid matrix upon cooling.

[0184] The cleaning adjunct(s) preferably comprise(s) from about 0.01%to about 10%, more preferably from about 0.02% to about 7%, even morepreferably from about 0.05% to about 5% by weight of the composition.

[0185] Methods

[0186] The fabric article treatment composition may be applied to astain, preferably a hydrophilic stain, on a fabric article in need oftreatment by any suitable means known in the art.

[0187] Nonlimiting examples of such methods of application includespraying, dipping, brushing, rolling and/or spreading.

[0188] With regard to the manner of using the spot pretreatmentcompositions, said compositions are typically used for the directtreatment of a soil or stained region of a textile or garment. Inaccordance with one aspect of the process according to the invention, asoiled garment is treated by applying an effective amount of the spotpretreatment composition directly at the location of a stain andoptionally onto the surrounding area of the stain. This can be done inone or more of the following ways. One way is simply by means ofmanually dispensing an effective amount of the spot pretreatmentcomposition directly from a container or vessel directly to the locationof the stain. To make such a manual application convenient for theconsumer, a number of devices may be used. For example, the spotpretreatment composition may be provided in a spray bottle having amanually operated pump, squeeze bottle, aerosol, or other dispensingcontainer. Such containers are known to the art. In such a way,localized application of the spot pretreatment composition isfacilitated and simplified by the requisite operation of the pump of thespray bottle, or by squeezing the squeeze bottle to dispense an amountof the spot pretreatment composition, or by spraying the cleaningcomposition from the pressurized aerosol container containing thecomposition according to the invention. A further particularly useful,known art dispensing apparatus is that of a container having a liquidpermeable applicator tip or end, such as a porous sponge or porousfabric applicator tip. In use, a removable cap covering the applicatortip is withdrawn, the container inverted to allow the flow of thecontainer's contents to impregnate the permeable applicator tip and thetip is then manually contacted with the stain to both transfer an amountof the spot pretreatment composition, and at the same time to manuallyagitate or abrade the textile or garment at the locus of the stain andoptionally in the surrounding region. Such manually applied agitationprovides a mechanical action which acts to physically break up thestain. This is particularly useful for stains which have been leftuntreated for an extended period of time, i.e., days, weeks, and longerperiods, and may have hardened. Such manual agitation, provides inaddition to the mechanical loosening of the stain, further acts toimprove the penetration of the spot pretreatment composition throughoutand among the stained fibers. Such mechanical action also improves theoverall stain removal characteristics of the spot pretreatmentcomposition. Due to these beneficial characteristics, containers havinga liquid permeable applicator tip or end is particularly preferred, andsuch containers are known to the art.

[0189] Typically, depending on the concentration of the surfactant blendused, the pre-treatment can be contacted with the stains for about 10 toabout 600 seconds, preferably about 20 to about 300 seconds. Typically,the material is sprayed or physically contacted with the soiled item. Inthe case of the use of a liquid material, common spray, nebulizer, orother equivalent that can apply the liquid material directly to thestain or spot can be used. In using the gel or solid formulations of theinvention, the solid gel, block or stick can be directly contacted withthe stain or spot leaving the solid formulation in the form of a thinfilm or residue substantially covering the entirety of any spot or stainon the garment. The pre-treated garment can be left to permit thesurfactant compositions of the formulation to associate with the stainto pre-treat the stain or spot outside the washing machine.

[0190] In another embodiment, fabric articles within a fabric articletreating apparatus may initially be contacted by a fabric articletreatment composition according to the present invention and thensubsequently contacted with a discrete lipophilic fluid. This processmay all occur in a hands-free manner within the apparatus itself.

[0191] In another embodiement, the method comprises the steps of:

[0192] a. contacting a fabric article in need of treatment with a fabricarticle treatment composition inside a fabric article treating apparatussuch that a stain on the fabric article is pretreated; and

[0193] b. subsequently contacting the fabric article with a discretelipophilic fluid such that the stain on the fabric article is removedand/or reduced.

[0194] The steps of contacting within the apparatus may be via automateddosing of the fabric article treatment composition and/or the discretelipophilic fluid by the apparatus.

[0195] All documents cited in the Detailed Description of the Inventionare, in relevant part, incorporated herein by reference; the citation ofany document is not to be construed as an admission that it is prior artwith respect to the present invention.

[0196] While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodification that are within the scope of this invention.

What is claimed is:
 1. A fabric article treatment compositioncomprising: a) a polar solvent exhibiting at least one of the followingHansen solubility parameters: i. a fractional polar value (f_(P)) ofgreater than 0.02; and/or ii. a fractional hydrogen bonding value(f_(H)) of greater than 0.10; and b) a hydrophobic surfactant; whereinthe fabric article treatment composition is miscible in a lipophilicfluid.
 2. The fabric article treatment composition according to claim 1wherein the polar solvent exhibits a fractional polar value (f_(P)) ofgreater than 0.05.
 3. The fabric article treatment composition accordingto claim 1 wherein the polar solvent exhibits a fractional hydrogenbonding value (f_(H)) of greater than 0.20.
 4. The fabric articletreatment composition according to claim 1 wherein the polar solvent isselected from the group consisting of: water, alcohols, glycols,polyglycols, ethers, carbonates, esters, ketones, other oxygenatedsolvents, amines, amides, ureas, alkanolamines, alkanolamides, phosphateesters, alkyl nitrites and mixtures thereof.
 5. The fabric articletreatment composition according to claim 4 wherein the polar solventcomprises from about 0% to about 50% by weight of the composition ofwater.
 6. The fabric article treatment composition according to claim 5wherein the polar solvent comprises from about 0.01% to about 20% byweight of the composition of water.
 7. The fabric article treatmentcomposition according to claim 4 wherein the polar solvent comprises aglycol and/or polyglycol and/or derivatives thereof.
 8. The fabricarticle treatment composition according to claim 4 wherein the polarsolvent comprises an alkoxy alcohol.
 9. The fabric article treatmentcomposition according to claim 1 wherein the composition comprises fromabout 2% to about 50% by weight of the composition of the hydrophobicsurfactant.
 10. The fabric article treatment composition according toclaim 9 wherein the composition comprises from about 10% to about 30% byweight of the composition of the hydrophobic surfactant.
 11. The fabricarticle treatment composition according to claim 1 wherein thehydrophobic surfactant exhibits an HLB value of from about 0.1 to about12.
 12. The fabric article treatment composition according to claim 11wherein the hydrophobic surfactant exhibits an HLB value of from about 3to about
 9. 13. The fabric article treatment composition according toclaim 1 wherein the hydrophobic surfactant is selected from the groupconsisting of: silicone-based surfactants, organosulfosuccinatesurfactants, alkanolamines, alkanolamides, alcohol alkoxylates, geminisurfactants, polyhydroxy fatty acid amides, alkylhydrogen phosphates andsalts thereof, saccharide derivatives and mixtures thereof.
 14. Thefabric article treatment composition according to claim 1 wherein thecomposition further comprises a cleaning adjunct and/or a lipophilicfluid.
 15. The fabric article treatment composition according to claim 1wherein the composition exhibits a flash point of greater than 37° C.16. The fabric article treatment composition according to claim 1further comprises a carrier solvent selected from the group consistingof: silicone solvents, hydrofluoroether solvents, perfluorinatedsolvents, hydrocarbon solvents, halogenated hydrocarbons, and mixturesthereof.
 17. An article of manufacture comprising: a. a container; andb. a fabric article treatment composition according to claim 1 containedwithin the container.
 18. A method for removing a hydrophilic stain froma fabric article in need of treatment, the method comprising contactingthe hydrophilic stain with a fabric article treatment composition thatis miscible in a lipophilic fluid to form a pretreated fabric article.19. The method according to claim 18 wherein the method furthercomprises contacting the pretreated fabric article with a lipophilicfluid such that the hydrophilic stain is removed and/or reduced.
 20. Themethod according to claim 18 wherein the pretreated fabric article isformed inside a fabric article treating apparatus.
 21. The methodaccording to claim 18 wherein the pretreated fabric article is formedprior to placing the fabric article inside a fabric article treatingapparatus.
 22. The method according to claim 18 wherein the hydrophobicfabric article treatment composition comprises: a) a polar solventexhibiting at least one of the following Hansen solubility parameters:i) a fractional polar value (f_(P)) of greater than 0.02; and/or ii) afractional hydrogen bonding value (f_(H)) of greater than 0.10; and b) ahydrophobic surfactant; wherein the hydrophobic fabric article treatmentcomposition is miscible in a lipophilic fluid.
 23. The method accordingto claim 18 wherein the hydrophobic fabric article treatment compositioncomprises a lipophilic fluid.
 24. A fabric article treated by the methodaccording to claim
 18. 25. A fabric article treatment compositioncomprising: a) from about 50% to about 70% by weight of the fabricarticle treatment composition of a first polar solvent; b. from about10% to about 30% by weight of the fabric article treatment compositionof a second polar solvent different from the first; c. from about 10% toabout 30% by weight of the fabric article treatment composition of ahydrophobic surfactant; and d. optionally, from about 3% to about 10% byweight of the fabric article treatment composition of a dispersantpolymer; wherein the fabric article treatment composition is miscible ina lipophilic fluid.
 26. The fabric article treatment compositionaccording to claim 25 wherein the first polar comprises3-methoxy-3-methyl-1-butanol.
 27. The fabric article treatmentcomposition according to claim 25 wherein the second polar compriseswater.